WO2017150908A1 - Procédé de formation d'un film de revêtement ayant une résistance à la chaleur élevée, une dureté et une résistance à l'abrasion élevées, film de revêtement ayant une résistance à la chaleur élevée, une dureté et une résistance à l'abrasion élevées, et outil de coupe comprenant celui-ci - Google Patents

Procédé de formation d'un film de revêtement ayant une résistance à la chaleur élevée, une dureté et une résistance à l'abrasion élevées, film de revêtement ayant une résistance à la chaleur élevée, une dureté et une résistance à l'abrasion élevées, et outil de coupe comprenant celui-ci Download PDF

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Publication number
WO2017150908A1
WO2017150908A1 PCT/KR2017/002254 KR2017002254W WO2017150908A1 WO 2017150908 A1 WO2017150908 A1 WO 2017150908A1 KR 2017002254 W KR2017002254 W KR 2017002254W WO 2017150908 A1 WO2017150908 A1 WO 2017150908A1
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Prior art keywords
layer
coating film
carbon
metal nitride
carbon content
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PCT/KR2017/002254
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English (en)
Korean (ko)
Inventor
이희수
전설
류지승
김부영
조승현
홍은표
김양도
Original Assignee
부산대학교 산학협력단
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Priority claimed from KR1020160024989A external-priority patent/KR101741948B1/ko
Priority claimed from KR1020160099072A external-priority patent/KR101793833B1/ko
Application filed by 부산대학교 산학협력단 filed Critical 부산대학교 산학협력단
Priority to US16/081,660 priority Critical patent/US10597781B2/en
Priority to JP2018546453A priority patent/JP6735841B2/ja
Publication of WO2017150908A1 publication Critical patent/WO2017150908A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
    • C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
    • C23C8/64—Carburising
    • C23C8/66—Carburising of ferrous surfaces
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C23C16/515—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using pulsed discharges
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B26—HAND CUTTING TOOLS; CUTTING; SEVERING
    • B26D—CUTTING; DETAILS COMMON TO MACHINES FOR PERFORATING, PUNCHING, CUTTING-OUT, STAMPING-OUT OR SEVERING
    • B26D1/00—Cutting through work characterised by the nature or movement of the cutting member or particular materials not otherwise provided for; Apparatus or machines therefor; Cutting members therefor
    • B26D1/0006—Cutting members therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/14—Layered products comprising a layer of synthetic resin next to a particulate layer
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/06—Surface hardening
    • C21D1/09—Surface hardening by direct application of electrical or wave energy; by particle radiation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5846—Reactive treatment
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32—Carbides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/36—Carbonitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/341—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one carbide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/60—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes
    • C23C8/62—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using solids, e.g. powders, pastes only one element being applied
    • C23C8/64—Carburising

Definitions

  • the present invention relates to a method for forming a high heat resistant, high hardness and wear resistant coating film, a high heat resistant, high hardness and wear resistant coating film, and a cutting tool comprising the same.
  • the machining process has been developed by high speed dry processing (excluding cutting oil or coolant) for high processing speed.
  • high speed dry cutting excluding cutting oil or coolant
  • Cutting tools used for high-speed dry processing of such difficult materials should be secured with high hardness and thermal shock resistance, thereby extending the life of the cutting tools by introducing a ceramic-based high hardness coating on the surface.
  • Titanium-based nitride the most widely used ceramic material used for high-hardness coating, has the advantage of high hardness due to covalent bonding and excellent adhesion to the metal base material.
  • TiN titanium nitride
  • TiZrN coatings which are particularly excellent in phase stability at high temperature and high pressure, are used.
  • Titanium-based nitride has problems such as surface degradation and coating layer peeling due to lattice expansion due to oxidation and phase change of "TiN" to titanium dioxide (TiO 2 ).
  • One object of the present invention is to provide a method of forming a coating film having high thermal shock resistance and improved surface hardness and wear resistance.
  • Another object of the present invention is to provide a high heat resistance, high hardness and wear resistant coating film.
  • Yet another object of the present invention is to provide a cutting tool comprising a high heat resistant, high hardness and wear resistant coating film.
  • Method for forming a high heat resistance, high hardness and wear-resistant coating film comprising a metal nitride layer and a carburized layer for one purpose of the present invention comprises the steps of forming a metal nitride layer on the metal base material; Forming a carbon layer on the metal nitride layer; And irradiating a laser to the carbon layer to form a carburized layer to which carbon is added as part of the metal nitride layer.
  • the metal nitride layer may include at least one of zirconium (Zr) and chromium (Cr) and titanium (Ti).
  • the forming of the carburized layer may be performed by irradiating the carbon layer with a pulse or continuous wave laser.
  • the carburized layer may include titanium carbide (TiC).
  • the carburized layer comprises a high carbon content; And a low carbon content portion disposed between the metal nitride layer remaining after the carburization and the high carbon content portion, and having a lower carbon content per unit area than the high carbon content portion.
  • the high carbon content portion may include titanium carbide (TiC).
  • the forming method may further comprise the step of removing the carbon layer remaining after the step of forming the carburized layer.
  • the carbon layer may be formed of graphite or carbon nanotubes (CNT).
  • the forming of the carbon layer may include coating a carbon paste including a carbon material, a binder, and a solvent on the metal nitride layer.
  • the size of the graphite may be 1 nm or more and 20 ⁇ m or less.
  • the forming method further comprises the step of forming a titanium layer on the metal base material before forming the metal nitride layer, the titanium of the titanium layer is nitrided in the process of forming the metal nitride layer
  • An adhesion improving layer made of titanium nitride (TiN) may be formed.
  • High heat resistance, high hardness and low friction coating film for another object of the present invention is formed on a metal base material, a metal nitride layer containing at least one of zirconium (Zr) and chromium (Cr) and titanium (Ti); And a carburized layer disposed on the metal nitride layer and including carburized metal nitride.
  • the carburized layer may include titanium carbide (TiC).
  • the carburized layer comprises a high carbon content; And a carbon low content part disposed between the metal nitride layer and the high carbon content part and having a carbon content less per unit area than the high carbon content part.
  • the high carbon content portion may include titanium carbide (TiC).
  • the coating film may further include an adhesion improving layer including titanium nitride (TiN) between the metal base material and the metal nitride layer.
  • TiN titanium nitride
  • the carburized metal nitride may include a compound in which carbon is inserted into the metal nitride in at least one of substituted and invasive forms.
  • the high heat resistance, high hardness and low friction coating film is formed on the surface of the metal base material, the coating film is a metal nitride layer; And a carbon-containing portion disposed on the metal nitride layer, and having a high carbon content portion, and including a carburized titanium nitride between the high carbon content portion and the metal nitride layer, wherein the carbon content per unit area is higher than that of the high carbon content portion.
  • This low carbon low content part comprises a carburized layer disposed.
  • the high heat, high hardness and wear resistant coating film and a cutting tool including the same the thermal shock resistance, the surface hardness and the wear resistance of the coating film can be improved. Since the coating film is coated on the metal base material, the life of the product corresponding to the metal base material can be extended.
  • FIG. 1 is a cross-sectional view for explaining a high heat resistance, high hardness and wear-resistant coating film according to an embodiment of the present invention.
  • FIG. 2 is a view for explaining a method of forming a coating film of FIG.
  • FIG. 3 is a diagram illustrating an XRD pattern of Sample 1a and Comparative Sample 1a.
  • FIG. 6 is a diagram for explaining a difference in concentration between carbons of Sample 1 and Comparative Sample 1a.
  • FIG. 6 is a diagram for explaining a difference in concentration between carbons of Sample 1 and Comparative Sample 1a.
  • FIG. 7 is a view for explaining the structural analysis results for each manufacturing process of Sample 1b according to the present invention.
  • FIG. 1 is a cross-sectional view for explaining a high heat resistance, high hardness and wear-resistant coating film according to an embodiment of the present invention.
  • a coating film including a metal nitride layer 310 and a carburized layer 320 including a transition metal is formed on a surface of the metal base material 100 according to the present invention.
  • the metal base material 100 is a metal base material formed of a metal, and the metal base material 100 itself may be formed of a metal, or the uppermost surface may be the metal base material 100 by including a metal layer.
  • the metal base material 100 may be a cutting tool.
  • the coating film is formed on the surface of the metal base material 100, the metal nitride layer 310 may improve the heat resistance of the coating film.
  • the metal nitride layer 310 of the coating film includes titanium (Ti) as a transition metal, and further includes zirconium (Zr) or chromium (Cr).
  • the heat resistance of the entire coating layer may be improved by the metal nitride layer 310.
  • the metal nitride constituting the metal nitride layer 310 may be a compound represented by Ti 1-x M x N (0 ⁇ x ⁇ 1, where M represents Zr or Cr).
  • the coating layers 310 and 320 themselves may be formed due to the lattice deformation and the increase in the bond between the zirconium or chromium and the nitrogen atoms, as compared with the case of the titanium nitride layer 310. The mechanical properties and heat resistance of the can be improved.
  • the carburized layer 320 is disposed on the metal nitride layer 310, and the surface hardness and the wear resistance may be improved by the carburized layer 320.
  • the carburized layer 320 is a layer formed by carburizing carbon in a metal nitride and includes “carburized metal nitride”.
  • the carburized layer 3200 may include titanium carbide (TiC).
  • Carbon (C) included in the carburized layer 320 is replaced with nitrogen (N) included in the metal nitride, that is, chemically bonded to the metal directly (substituted), or carbon (C) invading the metal nitride. May exist in an intervening form.
  • the component of the carburized layer 320 made of substituted and / or invasive carburized metal nitride is Ti 1-x M x (C y N 1-y ) [where 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1 ].
  • Ti 1-x M x (C y N 1-y ) means including at least one of nitride, carbide, and nitride carbide.
  • the carburized metal nitride may have an amorphous phase.
  • the carbon included in the “content of carbon” is defined to include both carbon intercalated and carbon intercalated into a metal nitride.
  • the carburized layer 320 may include a high carbon content 324 and a low carbon content 322.
  • the high carbon content portion 324 is a surface portion of the carburized layer 320 corresponding to the upper portion of the carburized layer 320 and substantially corresponds to the surface of the coating layer.
  • the carbon content included in the high carbon content portion 324 is greater than the carbon content included in the carbon low content portion 322 per unit area. In this case, in the carbon content, the high carbon content portion 324 may be at least 1.5 times or more than the low carbon content portion 322.
  • Titanium carbide (TiC) included in the carburized layer 320 is a component mainly included in the high carbon content 324.
  • the high carbon content portion 324 is a carburized metal nitride, titanium nitride, titanium carbide, zirconium nitride, zirconium carbide, zirconium nitride, titanium nitride It may further include at least one of zirconium, titanium carbide-zirconium, titanium carbide-zirconium, and invasive carbon.
  • the high carbon content 324 may include titanium nitride, titanium nitride, chromium nitride, chromium carbide, chromium nitride, titanium nitride-chromium, carbon titanium-chromium, It may further comprise at least one of titanium nitride-chromium and interstitial carbon.
  • titanium carbide (TiC) is significantly higher than these components, so that titanium carbide (TiC) is the main component of the high carbon content portion 324 Can be.
  • the low carbon content 322 is a layer interposed between the high carbon content 324 and the metal nitride layer 310, including carburized metal nitride, compared to the carbon content per unit area of the high carbon content 324 Has a low content.
  • the metal nitride layer 310 further includes chromium or zirconium based on titanium, thereby improving mechanical properties and heat resistance of the coating layer.
  • the carburized layer further includes carbon, thereby chemically bonding titanium to carbon.
  • an adhesion improving layer 201 may be disposed between the coating film and the metal base material 100.
  • the adhesion improving layer 201 may include titanium nitride (TiN), and may be interposed between the metal base material 100 and the metal nitride layer 310.
  • the adhesion improving layer 201 may improve the adhesion between the coating film and the metal base material 100.
  • the coating film including the metal nitride layer 310 and the carburized layer 320 is formed on the surface of the metal base material 100, not only the heat resistance of the metal base material 100 but also the surface hardness and wear resistance Can improve.
  • FIG. 2 is a view for explaining a method of forming a coating film of FIG.
  • an adhesion improving layer 201 and a nitride layer 300 are formed on a metal base material 100, and a carbon layer is formed on the metal base material 100 on which the nitride layer 300 is formed.
  • a carbon layer is formed on the metal base material 100 on which the nitride layer 300 is formed.
  • a titanium layer is formed on the metal base material 100, and the nitride layer 300 is formed on the metal base material 100 on which the titanium layer is formed.
  • SUS or WC-Co (tungsten carbide-cobalt) substrate can be used as the metal base material 100.
  • the nitride layer 300 titanium and a transition metal are provided as target materials, and at the same time, nitrogen gas is supplied.
  • the titanium layer is nitrided with titanium nitride (TiN) by the supplied nitrogen gas to improve adhesion.
  • 201 may be formed.
  • the components of the formed nitride layer 300 are substantially the same as the metal nitride layer 310 including the transition metal described with reference to FIG. 1, and part of the nitride layer 300 is carburized, and the remainder remains to form the metal nitride layer 310.
  • the nitride layer 300 may be formed by physical vapor deposition.
  • the nitride layer 300 may be deposited by RF / DC magnetron sputtering.
  • the formation of a separate adhesion improving layer 201 is omitted, and after cleaning the surface of the metal base material 100, the nitride layer formed thereon through the surface treatment of the cleaned metal base material 100 ( Adhesion with 300 can be improved. Surface treatment can be carried out using ion bombardment.
  • the washing process may be washed with ethanol and / or acetone and may be performed at least once.
  • the nitride layer 300 may be formed by depositing a sintered compound target on the surface of the metal base material 100 by using an arc discharge technique sputtering. During the deposition process, the temperature of the metal base material 100 may be maintained at 330 ° C to 370 ° C for grain growth in the nitride layer 300.
  • the nitride layer 300 formed as described above is substantially the same as the metal nitride layer 310 including titanium described above with reference to FIG. 1 but further including zirconium or chromium, and part of the nitride layer 300 is carburized. The remainder remains to form the metal nitride layer 310.
  • a carbon layer 400 is formed thereon.
  • the carbon paste includes a carbon material, a binder, and a solvent.
  • Graphite or carbon nanotubes (CNT) may be used as the carbon material, and the carbon material may be distributed in a mixture of the binder and the solvent to form a carbon paste.
  • the carbon paste contains graphite, it is preferable to use those having a size of 20 ⁇ m or less.
  • the carbon paste includes graphite having a size of 20 ⁇ m or less, there is an advantage that the mechanical properties of the coating layer can be significantly improved as compared with the case of using a larger size of graphite.
  • the binder may be polyvinylidene difluoride (PVDF).
  • the solvent may be N-methyl-2-pyrrolidone (N-methyl-2-pyrrolidone, NMP).
  • NMP N-methyl-2-pyrrolidone
  • the weight ratio of the carbon material and PVDF is 90:10, and the viscosity can be controlled by adding a small amount of the solvent.
  • the carbon layer 400 may be formed by uniformly spreading the carbon paste with a brush or a spatula (brushing process) or by spraying the carbon paste (spray process), and drying it.
  • the drying process may be performed at a temperature of 100 ° C. to 150 ° C. for 15 minutes to 1 hour.
  • the adhesion of the carbon layer 400 may be improved to prevent the carbon layer 400 from being peeled off from the surface of the nitride layer 300, and the carbon layer 400 in the carburization process using a laser afterwards.
  • the surface of the carbon layer 400 may be smoothed through the drying process of the carbon layer 400.
  • a carburization process is performed using a laser.
  • the carburization process is laser ablation, in which carbon in the carbon layer 400 is a carbon source injected into the nitride layer 300, and carburization occurs by laser irradiation.
  • the carburization process may be performed in one direction from one end of the metal base material 100 toward the other end, and may be performed at least once.
  • the laser can be performed through pulses or continuous waves. In the case of using a pulse laser, it is possible to specify the frequency of the band of 3 Hz to 20 Hz. In addition to the frequency, the thickness of the carburized layer 320 or the carbon content of the carburized layer 320 may be determined by adjusting the output of the laser and / or the number of irradiation of the laser.
  • the high content portion 324 is formed, and a part of the nitride layer 300 remains as the metal nitride layer 310 described with reference to FIG. 1.
  • the high carbon content portion 324 and the low carbon content portion 322 constitute the carburized layer 320 to protect the surface of the metal base material 100 together with the metal nitride layer 310 to protect the surface of the metal base material 100. It is possible to configure a coating film that can improve the mechanical properties.
  • a cleaning process for additionally removing the remaining carbon layer 400 may be performed.
  • the cleaning process may be performed by ultrasonic cleaning using a solvent. For example, it can be performed by first washing with ethanol and second washing with acetone, and the first and second washes can be repeated.
  • the coating film including the metal nitride layer 310 and the carburized layer 320 is formed on the surface of the metal base material 100, not only the heat resistance of the metal base material 100 but also surface hardness and wear resistance Can improve.
  • Ti 0.7 Zr 0.3 N was deposited to 3.0 ⁇ m under the deposition conditions shown in Table 1 below.
  • the Ti layer was converted to TiN by the nitrogen gas provided in the step of forming the Ti 0.7 Zr 0.3 N layer, and Ti 0.7 Zr 0.3 N was formed thereon.
  • Ti Zr ratio (at.%) Of target materials 70:30 Base pressure (Torr) 1.0 x 10 -5 Working pressure (Torr) 1.0 x 10 -2 RF power (W) 200 Deposition temperature (K) 723 Deposition time (h) 6.0 Rotational velocity of substrate (rpm) 15 Ar: N2 gas ratio 5: 1 Coating thickness ( ⁇ m) 3.0
  • a carbon paste was hand-brushed using a spatula to form a 0.2 mm thick graphite layer.
  • a weight ratio of graphite having a size of 20 ⁇ m to PVDF of 90:10 was used as a solvent for viscosity control as NMP.
  • the coated graphite layer was dried at 130 ° C. for about 10 minutes, and then scanned with laser in one direction at 60% power at 5 Hz using LSX-213 (trade name, CETAC technologies) using Nd-YAG as a light source. The process was carried out 10 times.
  • a TiN layer and a Ti 0.7 Zr 0.3 N layer were sequentially formed on SUS304 to prepare Comparative Sample 1a without a carburized layer.
  • the manufacturing process of the TiN layer and the Ti 0.7 Zr 0.3 N layer was performed substantially the same as the manufacturing process of Sample 1a.
  • FIG. 3 is a diagram illustrating an XRD pattern of Sample 1a and Comparative Sample 1a.
  • FIG. 3 shows the XRD pattern of Comparative Sample 1
  • (b) shows the XRD pattern of Sample 1a
  • the x-axis shows the diffraction angle (2 ⁇ , unit ⁇ ).
  • the major peaks appear at the same diffraction angle in both the sample 1a and the comparative sample 1a. Through this, it can be seen that the main peak does not appear by laser ablation. However, in the case of the sample 1a in which the graphite layer was formed and the laser ablation was performed, it was confirmed that a lot of noise occurred in the first half compared to the comparative sample 1a. Due to such noise generation, it can be expected that amorphousness occurred on the surface by laser irradiation and carburization by laser ablation at the time of manufacture of the sample 1a, and it can be seen that the mechanical properties of the coating layer were improved due to the amorphousness.
  • Comparative Samples 1b to 1e were prepared through substantially the same process as the preparation of Comparative Sample 1a, and Knoop hardness (Knoop, HK) was measured for each.
  • the laser was irradiated 20 times at 50% power and 5 Hz for each of Comparative Samples 1b to 1e to prepare Samples 2-1, 3-1, 4-1 and 5-1, respectively, and then Knoop hardness. was measured. Furthermore, lasers were repeatedly irradiated 10 times at a frequency of 60% at 10 Hz for the same samples as Comparative Samples 2 to 5 to prepare Samples 2-2, 3-2, 4-2, and 5-2, respectively. , Knoop hardness was measured.
  • Knob hardness is measured 12 times for each area of each sample and is expressed as the average of 10 hardness values excluding maximum and minimum values.
  • Characteristic evaluation-2 evaluation of wear resistance characteristics
  • FIG. 6 is a view for explaining a difference in concentration between carbons of sample 1a and comparative sample 1a.
  • the x-axis represents the distance from the surface to the measurement point, i.e. the depth
  • the intensity of the y-axis represents the concentration of carbon
  • "After ablation” is for sample 1a
  • "Before ablation” is for comparative sample 1a. It is about.
  • the carbon concentration on the surface of sample 1a is generally higher than the carbon concentration on the surface of comparative sample 1a.
  • the carbon content increased on the surface, through which the carburized layer was formed in the sample 1a it can be seen that the carbon content significantly increased due to the presence of TiC in the surface carbonization of the carburized layer. Due to the formation of this carburized layer, it can be expected that the mechanical properties of Sample 1a are improved compared to Comparative Sample 1.
  • Sample 1b according to the present invention was prepared in the same manner as Sample 1a, except that a Ti 0.5 Zr 0.5 N layer was formed using an atomic ratio of Ti to Zr of 50:50.
  • Sample 1c was prepared by substantially the same process as the preparation of sample 1a, except that carbon nanotubes were used instead of graphite in the carbon paste.
  • Sample 2 was prepared through a process substantially the same as the preparation of sample 1a, except that the spraying process was used instead of the brushing process in forming the carbon layer.
  • a TiN layer and a Ti 0.5 Zr 0.5 N layer were sequentially formed on SUS304 to prepare Comparative Sample 2 without a carburized layer.
  • the manufacturing process of the TiN layer and the Ti 0.5 Zr 0.5 N layer was performed substantially the same as the manufacturing process of Sample 1b.
  • FIG. 7 is a view for explaining the structural analysis results for each manufacturing process of Sample 1b according to the present invention.
  • FIG. 7 shows the k 3 ⁇ EXAFS data at Ti K-edge for titanium-zirconium nitride before carbon is added, and (b) shows the Fourier transform EXAFS data.
  • C shows k 3 ⁇ EXAFS data at Ti K-edge before and after carbon addition to titanium-zirconium nitride, and (d) shows Fourier transform EXAFS before and after carbon addition to titanium-zirconium nitride. Data is shown.
  • the x axis represents time (unit: seconds) and the y axis represents friction coefficient.
  • (a) relates to sample 1c and (b) relates to sample 1b.
  • the friction coefficients of the samples 1b and 2 using graphite may be confirmed to be substantially unchanged.
  • the coefficient of friction increases after 100 seconds, but it is confirmed that there is no substantial change before that.
  • Comparative Sample 2 that does not include the carburized layer, the friction coefficient gradually increases from 30 seconds, and then the friction coefficient rapidly increases around 100 seconds. That is, in case of Comparative Sample 2, deterioration occurs at a maximum of about 50 seconds, but in case of Sample 1c, deterioration occurs after 150 seconds, and in case of Samples 1b or 2, there is no substantial change even if time elapses up to 300 seconds. You can check it.
  • Sample 3 was prepared in the same manner as in the preparation of Sample 1b, except that WC-Co was used as the metal matrix instead of SUS304 and chromium was used instead of zirconium.
  • sample 4 was prepared by following the same process as preparing sample 2, except that chromium was used instead of zirconium.
  • the graph relates to the surface friction coefficient characteristics for samples 3, 4 and comparative sample 3, the SEM photograph (a) is for comparative sample 3, and (b) is for sample 3.

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Abstract

La présente invention concerne un procédé de formation d'un film de revêtement ayant une résistance à la chaleur élevée, une dureté et une résistance à l'abrasion élevées, un film de revêtement ayant une résistance à la chaleur élevée, une dureté et une résistance à l'abrasion élevées, et un outil de coupe comprenant celui-ci, et le procédé de formation d'un film de revêtement comprend les étapes de : formation d'une couche de nitrure métallique sur une base métallique; formation d'une couche de carbone sur la couche de nitrure métallique; et formation, par émission d'un laser au niveau de la couche de carbone, une couche de carburation comportant du carbone ajouté à une partie de la couche de nitrure métallique.
PCT/KR2017/002254 2016-03-02 2017-03-02 Procédé de formation d'un film de revêtement ayant une résistance à la chaleur élevée, une dureté et une résistance à l'abrasion élevées, film de revêtement ayant une résistance à la chaleur élevée, une dureté et une résistance à l'abrasion élevées, et outil de coupe comprenant celui-ci WO2017150908A1 (fr)

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US16/081,660 US10597781B2 (en) 2016-03-02 2017-03-02 Method for forming coating film having high heat resistance, high hardness and abrasion resistance, coating film having high heat resistance, high hardness and abrasion resistance, and cutting tool comprising same
JP2018546453A JP6735841B2 (ja) 2016-03-02 2017-03-02 高耐熱性、高硬度及び耐摩耗性コーティング膜の形成方法、高耐熱性、高硬度及び耐摩耗性コーティング膜及びこれを含む切削工具

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KR10-2016-0024989 2016-03-02
KR1020160024989A KR101741948B1 (ko) 2016-03-02 2016-03-02 고내열, 고경도 및 내마모성 코팅막의 형성 방법, 고내열, 고경도 및 내마모성 코팅막 및 이를 포함하는 절삭 공구
KR10-2016-0099072 2016-08-03
KR1020160099072A KR101793833B1 (ko) 2016-08-03 2016-08-03 고내열 및 고경도 질화물 코팅막의 내마모성 향상 방법, 코팅막 및 이를 포함하는 절삭 공구

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US11136672B2 (en) 2018-08-30 2021-10-05 Apple Inc. Electronic devices having corrosion-resistant coatings
CN114196921B (zh) * 2022-02-17 2022-04-22 中南大学湘雅医院 一种镁合金表面涂层及其制备方法

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CN114107881B (zh) * 2021-11-15 2023-07-25 湖南弘辉科技有限公司 一种高速风机叶片加工工艺

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